JPH0768113B2 - Cosmetic composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cosmetic composition for absorbing ultraviolet rays, which comprises at least one of a dehydroamino acid derivative and a benzalhydantoin derivative.

2. Description of the Related Art Ultraviolet rays are known to cause various changes in skin. In dermatology, ultraviolet rays are
0-320 nm), medium-wavelength ultraviolet light (320-290 nm), and short-wavelength ultraviolet light (290-100 nm), which are respectively called UV-A, UV-B, and UV-C.

Of these, UV-C is absorbed in the ozone layer and hardly reaches the ground. UV-B is more than a certain amount,
It is known that when the skin is irradiated, it causes erythema, blisters, and pigmentation. In contrast, UV-A
Has traditionally been said to cause less significant changes to the skin. However, recently it has been found from electron microscopy and histological evaluation that UV-A causes changes in elastic fibers in the blood vessel wall and connective tissue. In addition, it causes damage to sensitive skin and to skin that is constantly exposed to sunlight. It has also been reported that UV-A promotes the action of UV-B (J. Willis, A. Kligman, and J. Eps.
tein “Photo-enhancement” The Journal of Investigat
ive Dermatology 59, No. 6, 416, 1973), shielding UV-A is as important as shielding UV-B.

As the UV-B absorbent, a benzophenone-based absorbent, a salicylic acid-based absorbent, a cinnamic acid-based absorbent, a para-aminobenzoic acid-based absorbent, or the like is used. However, among the above-mentioned ultraviolet absorbers, very few have the effects, safety, solubility, stability and the like.

Also, the history of research on UV-A is short, and substances that effectively absorb UV-A when applied to the skin are not well known. Currently, only a few dibenzoylmethane derivatives, cinnamic acid derivatives and chalcone derivatives are known. (West German Patent Publication Nos. 2728241, 2728243, JP-A-51-61641, 52-46056, 57-59840, 57)
-197209, 60-109544) In addition to the above-mentioned ultraviolet absorbers, inorganic powders such as titanium dioxide, zinc oxide, and iron oxide, which have a function of physically reflecting and scattering ultraviolet rays, are also used.

Problems to be Solved by the Present Invention As described above, although various ultraviolet absorbers have been developed, ultraviolet absorbing ability, safety, solubility in solvents and resins,
It is the fact that nothing satisfying all of the above requirements and stability has yet been found, and thus an ultraviolet absorber and a cosmetic composition having excellent ultraviolet absorbing ability, safety and stability are desired.

Benzophenone-based absorbers have an absorption effect for long-wavelength ultraviolet rays of 320 to 400 nm, but have a relative absorption capacity for medium-wavelength ultraviolet rays (290 to 320 nm), which are considered to cause blistering. Very low.

Para-aminobenzoic acid-based and cinnamic acid-based absorbents have high absorption effects, but are said to have stability problems. Also,
The salicylic acid-based absorbent has a weak absorption effect and cannot be expected to be effective unless it is mixed in a large amount.

On the other hand, inorganic powders have a problem that the types of cosmetics that can be blended are limited and that they are colored when blended in a large amount.

Means for Solving the Problems In view of such circumstances, the inventors of the present invention have conducted diligent research, and as a result, have found that the α-dehydroamino acid derivative represented by the following general formula (1) and the benzene represented by the general formula (2). As shown in Table 1 and Table 2, the saarhydantoin derivative is 240-400.
It has been found that it has a large absorption effect on nm and is easily soluble in various animal and vegetable oils, oils and fats, and organic solvents. Among these compounds, a cosmetic composition characterized by containing at least one kind is effective in preventing erythema of the skin having a good UV absorption ability, and is excellent in light and heat stability, skin, lips, The present invention was completed by finding that it is not irritating or toxic to hair, nails and the like.

(However, B is a hydrogen atom or an acetyl group. X ₁ ,
X ₂ and X ₃ are either a hydrogen atom, a hydroxyl group, or a methoxy group, and two or three of them may be the same at the same time, or all of them may be different. Y is an oxygen atom or an amino group (-NH-). Z is a methyl group or a phenyl group. R is an alkyl group, a cyclohexyl group C ₃ -C _18, or a trimethylcyclohexyl group. ) (However, in the general formula 2, X ₁ , X ₂ , and X ₃ are hydrogen atoms, hydroxyl groups,
Alternatively, two or three of them may be the same at the same time, or all of them may be different. W is a hydrogen atom or a -CH ₂ -CH ₂ CO ₂ R. R
Is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group or a trimethylcyclohexyl group. ) The present invention also relates to other hair of the human epidermis against sunlight irradiation,
Provide a method to protect lips and nails. It has the general formula (1)
And (2) applying a cosmetic composition containing at least one of the indicated compounds to the skin, hair, lips and nails.

More specifically, to exemplify the compound of the general formula (1) used in the cosmetic composition of the present invention: N-benzoyl-O-
Methyl-α-dehydrotyrosine laurylamide, N-
Benzoyl-O-methyl-α-dehydrotyrosine isopropyl ester, N-benzoyl-O-methyl-α-
Dehydrotyrosine lauryl ester, N-benzoyl-O-methyl-α-dehydrotyrosine stearyl ester, N-benzoyl-O-methyl-α-dehydrotyrosine 2-ethylhexyl ester, N-benzoyl-
O-methyl-α-dehydrotyrosine cyclohexyl ester, N-benzoyl-O-methyl-α-dehydrotyrosine 3,3,5-trimethylcyclohexyl ester, N-acetyl-O-methyl-α-dehydrotyrosine isopropyl ester, N- Acetyl-O-methyl-
α-dehydrotyrosine 2-ethylhexyl ester,
N-acetyl-O-methyl-α-dehydrotyrosine lauryl ester, N-acetyl-O-methyl-α-dehydrotyrosine stearyl ester, N-acetyl-N
-Benzoyl-O-methyl-α-dehydrotyrosine n
-Butyl ester, N-acetyl-N-benzoyl-O
-Methyl-α-dehydrotyrosine isopropyl ester, N-acetyl-N-benzoyl-O-methyl-α-
Dehydrotyrosine 2-ethylhexyl ester, N-
Acetyl-N-benzoyl-O-methyl-α-dehydrotyrosine lauryl ester, N-acetyl-N-benzoyl-O-methyl-α-dehydrotyrosine stearyl ester, N, N-diacetyl-O-methyl-α-dehydrotyrosine n-butyl ester, N, N-diacetyl-O-methyl-α-dehydrotyrosine isopropyl ester, N, N-diacetyl-O-methyl-α-dehydrotyrosine 2-ethylhexyl ester, N, N
-Diacetyl-O-methyl-α-dehydrotyrosine lauryl ester, N, N-diacetyl-O-methyl-α
-Dehydrotyrosine stearyl ester, N-benzoyl-3,4,5-trimethoxy-α-dehydrophenylalanine 2-ethylhexyl ester and the like can be mentioned.

To exemplify the compound of the general formula (2) used in the cosmetic composition of the present invention: 4-benzylidene-2,5-dioxo-1,3-imidazolidinedipropionic acid, 4-benzylidene-2, 5-Dioxo-1,3-imidazolidine dipropionic acid diisopropyl ester, 4-benzylidene-2,5-dioxo-1,3-imidazolidine dipropionic acid di-n-butyl ester, 4-benzylidene-
2,5-Dioxo-1,3-imidazolidine dipropionic acid diisobutyl ester, 4-benzylidene-2,5
-Dioxo-1,3-imidazolidinedipropionic acid bis (2-ethylhexyl ester), 4-benzylidene-2,5-dioxo-1-imidazolidinepropionic acid, 4-benzylidene-2,5-dioxo-1-imidazo Lysine propionic acid isopropyl ester, 4-benzylidene-2,5-dioxo-1-imidazolidine propionic acid n-butyl ester, 4-benzylidene-
2,5-dioxo-1-imidazolidinepropionic acid
Isobutyl ester, 4-benzylidene-2,5-dioxo-1-imidazolidinepropionic acid 2-ethylhexyl ester, 4- (3,4-dimethoxyphenyl)
Methylene-2,5-dioxo-1,3-imidazolidine dipropionic acid, 4- (3,4-dimethoxyphenyl)
Methylene-2,5-dioxo-1,3-imidazolidine dipropionic acid dimethyl ester, 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1,3
-Imidazolidine dipropionic acid diethyl ester, 4
-(3,4-dimethoxyphenyl) methylene-2,5-
Dioxo-1,3-imidazolidine dipropionic acid diisopropyl ester, 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1,3-imidazolidine dipropionic acid di-n-butyl ester, 4-
(3,4-dimethoxyphenyl) methylene-2,5-dioxo-1,3-imidazolidine dipropionic acid diisobutyl ester, 4- (3,4-dimethoxyphenyl)
Methylene-2,5-dioxo-1,3-imidazolidine dipropionic acid bis (2-ethylhexyl ester),
4- (3,4-dimethoxyphenyl) methylene-2,5
-Dioxo-1-imidazolidinepropionic acid, 4-
(3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid isopropyl ester, 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid methyl ester Ester, 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid ethyl ester, 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazo Lysine propionic acid n-butyl ester, 4-
(3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid isobutyl ester, 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid 2 -Ethylhexyl ester, 4- (4-methoxyphenyl) methylene-2,5-dioxo-1-imidazoline propionic acid ethyl ester, 4- (3,4,5)
-Trimethoxyphenyl) methylene-2,5-dioxo-1-imidazoline dipropionic acid ethyl ester and the like.

The cosmetic composition according to the present invention has the above general formula (1) or /
And a compound represented by (2) and a conventionally known component, that is, an oil phase component or / and an aqueous phase component or /
And / or a powder component or / and a surfactant component that emulsifies, disperses or solubilizes them.

If these known ingredients used here are exemplified, for example, the oil phase ingredients include beeswax, wood wax, spermaceti wax, carnauba wax, candy wax, cocoa butter, cetyl alcohol, stearyl alcohol, oleic acid, stearic acid. , Lanolin, olive oil, camellia oil, cottonseed oil, castor oil, oleyl alcohol, squalane and other animal and vegetable oils, solid paraffin, ceresin, microcrystalline wax, petrolatum, liquid paraffin, silicone oil and other mineral oils, and isopropyl myristate, Examples include synthetic fats and oils such as synthetic polyethers. Further, as the aqueous phase component, glycerin, propylene glycol, sorbit, polyethylene glycol, quince seed gum, tran gum gum, alginate, pectin,
Carboxymethyl cellulose, hyaluronic acid, water-soluble chitin, polyvinyl alcohol, ethanol, isopropanol, citric acid, urea, cationized cellulose fatty acid polypeptide condensate, lactic acid, pyrrolidone carboxylate,
Examples include various amino acids. Further, if the surfactant used is exemplified, polyoxyethylene fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene glycene fatty acid partial ester, polyglycerin fatty acid partial ester, fatty acid alkanolamide, fatty acid alkanolamide Ethylene oxide adduct, polyoxyethylene glycerin fatty acid,
Pyroglutamic acid monoglycerin ester, nonionic activator such as acylglutamic acid glycerin ester, alkyl sulfate, polyoxyethylene alkyl sulfate, fatty acid amide ether sulfate, alkylbenzene sulfonate, alkyloxysulfonate, sulfosuccinic acid higher alcohol ester salt, N
-Long-chain fatty acid acyl-N-methyltaurine salt, fatty acid salt, N-long-chain acylglutamate, N-long-chain acylsarcosine salt, anionic active agent such as monoalkyl phosphate, carboxybetaine type, imidazoline type, lecithin , Amphoteric activators such as aminosulfonic acid type, alkylamine oxide type, Nα, Nα-dimethyl or Nα, Nα, Nα-trimethyl-Nε-acyl basic amino acid, dialkyldimethylammonium chloride, alkyltrimethylammonium chloride, fatty acid acylarginine Examples include cationic activators such as ethyl ester salts. As the powder component, talc, kaolin, titanium dioxide, titanium-coated mica, mica, iron oxide, silicic acid, ultramarine blue, navy blue, zinc white, clay, precipitated calcium carbonate and other inorganic powders, N-mono long-chain acyl Examples thereof include organic powders such as basic amino acids.

Further, these cosmetic compositions are usually used cosmetic aids such as thickeners, softeners, humectants, superfatting agents, emollients,
Wetting agents, preservatives, defoamers, fragrances, dyes and / or fragrances which may be used for coloring the composition itself or the skin, or any other ingredient normally used in cosmetics may be included.

The cosmetic composition of the present invention can take any form such as a solution, an emulsion, a kneaded mixture, a solid (pressed product), a powder, etc. by adjusting the types of the above-mentioned components and the blending amounts thereof. Is possible. Further, the use of the cosmetic composition of the present invention includes sun oil, lotion, cream, emulsion, air conditioner, hair conditioner, liquid foundation, lipstick, foundation,
White powder, aerosol, etc.

The content of the compounds of the general formulas (1) and (2) in the cosmetic composition of the present invention varies depending on the composition and the required sun protecting factor (SPF), but in general,
It is 0.1 to 20% by weight, preferably 0.5 to 10% by weight.

As the ultraviolet absorber contained in the cosmetic composition of the present invention, one kind of the compounds represented by the general formulas (1) and (2) may be used alone, or some of them may be combined. Further, at least one of the compounds represented by the general formulas (1) and (2) may be used in combination with another ultraviolet absorber.

Suitable UV absorbers for this purpose include, for example, camphor derivatives such as p-methylbenzylidene-DL-camphor or its sulfonic acid sodium salt, 2-phenylbenzimidazole-5-sulfonic acid sodium salt, 3, 4
-Dimethylphenylglyoxylic acid sodium salt, 4-
Benzophenones such as phenylbenzophenone-2-carboxylic acid isooctyl ester, p-methoxycinnamic acid ester, 2-phenyl-5-methylbenzoxazole, salicylic acid 2-ethylhexyl ester or p-
Examples thereof include dimethylaminobenzoic acid esters.

It can also be used together with an inorganic powder such as titanium dioxide as a light shielding agent.

The compound of the general formula (1) is hippuric acid and derivatives thereof,
Made from aromatic aldehydes and acid chlorides. The compound of general formula (2) can be prepared from readily available industrial starting materials such as hydantoin, aromatic aldehydes, and acrylic acid esters.

EFFECTS OF THE INVENTION The α-dehydroamino acid derivative represented by the general formula (1) and the benzalhydantoin derivative represented by the general formula (2) have a large absorption effect at 240 to 400 nm and can be used for various animal and vegetable oils, oils and organic solvents. Is also easily soluble. Among the benzalhydantoin derivatives represented by the general formula (2), those in which X ₂ is a hydroxyl group or a methoxy group are particularly suitable for a long wavelength region (32
It has a large absorption at 0-400 nm) and is soluble in various animal and vegetable oils, fats and organic solvents. These α-dehydroamino acid derivatives and benzalhydantoin derivatives are excellent materials having good ultraviolet absorption ability, excellent light and heat stability, and neither irritating nor toxic to skin, hair and mucous membranes. Therefore, by blending 0.1 to 20% of these compounds depending on the application, various oils, lotions, creams, emulsions, hair rinses, hair conditioners, liquid foundations, lipsticks, foundations, white powders, cosmetic compositions such as aerosols can be obtained. Can be provided.

Next, the maximum absorption wavelength (λ _max ), the molar extinction coefficient (ε _max ) and other physical property values of the representative compounds according to the present invention are collectively shown in Table 1 and Table 2 as Example 1. In addition, although typical formulation examples are shown in Example 2 and the following, the present invention is not limited to these Examples.

Example 2 Sun oil A sun oil was prepared by blending the following composition according to a conventional method. More advantageous conditions for homogenizing the composition below are about 40 to
Mixing while heating to 45 ° C.

N- acetyl -N- benzoyl -O- methyl -α- Dehidorochi 4 wt% core 2-ethylhexyl an ester cocoa butter 2.5 wt% Perfume 0.5 wt% triglyceride 93 wt% (C ₈ ~C ₁₂₎ Example 3 Skin Protection Cream (O / W type) Each of the components (A) and (B) was heated and dissolved according to the following composition. After mixing both, it cooled to room temperature and prepared the skin protection cream.

(A) 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1,3-imidazolidine 8% by weight dipropionic acid diethyl ester N, N-diacetyl-O-methyl-α- dehydroepiandrosterone tyrosine y 8 wt% isopropyl ester fatty acid triglycerides 10% by weight (C ₈ -C ₁₂₎ cetyl alcohol 1.5 wt% polyoxyethylene cetyl ether and polyoxyethylene stearyl ether 6 wt% (10E.O.) monostearate Polyoxyethylene sorbitan 2% by weight (20E.O.) (B) Glycerin 1.5% by weight Propylene glycol 1.5% by weight Sorbitol solution (70%) 3.5% by weight Pyrrolidonecarboxylic acid sodium salt 0.5% by weight Methyl paraoxybenzoate 0.2% by weight Water 57.3% by weight Example 4 Skin protection cream (W / O type) The following composition was used as in Example 3. Was prepared skin protection cream formulated according to the method.

(A) N-benzoyl-O-methyl-α-dehydrotyrosine 2-d 8% by weight tylhexyl ester cetyl alcohol 1.5% by weight beeswax 1.5% by weight paraffin oil 3% by weight cholesterol 1% by weight fatty acid triglyceride 8% by weight (C ₈ ~ C ₁₂ ) Glycerin monostearate 5% by weight Sorbitan monopalmitate 9% by weight Polyoxymonostearate ethylene sorbitan 1% by weight (20E.O.) Ceresin 5% by weight Whale wax 2% by weight Propyl paraoxybenzoate 0.1% by weight (B) ) Glycerin 1.5% by weight Propylene glycol 1.5% by weight Sorbitol solution (70%) 4% by weight Methyl paraoxybenzoate 0.2% by weight Water 47.7% by weight Example 5 Sun milk (milky lotion) The following composition was blended according to the same method as in Example 3. The sun milk was prepared.

(A) 4-benzylidene-2,5-dioxo-1,3-imidazolidindipropionic acid diisopropionate 5% by weight ruester 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazo Lysine propionate 2-ethylhexyl 2% by weight ester Polyoxyethylene cetyl ether and stearyl ether 5% by weight (10E.O.) Vaseline oil 6% by weight Isopropyl myristate 3% by weight Silicone oil 1% by weight Cetyl alcohol 1% by weight Preservative proper amount fragrance proper amount water balance Example 6 Sun milk (milky lotion) The following composition was blended in the same manner as in Example 3 to prepare sun milk.

(A) 4-benzylidene-2,5-dioxo-1-imidazolidinepropionate isopropyl ester 5% by weight le liquid paraffin 22.6% by weight solid paraffin 4.5% by weight cetanol 4% by weight sorbitan monostearate 1.8% by weight monostearin Acid polyoxy ethylene sorbitan 2.8% by weight (20E.O.) Nε-cocoyl ornithine 5% by weight (B) Pyrrolidonecarboxylic acid triethanolamine salt 4% by weight water 50.1% by weight Preservative 0.2% by weight Example 7 sunscreen lotion The following composition According to the procedure described above, the component (A) was dissolved by heating and cooled to room temperature, and then the component (B) was added to prepare a sunscreen lotion.

(A) 4-benzylidene-2,5-dioxo-1,3-imidazolidindipropionate dinatriu 2% by weight mu salt glycerin 5% by weight polyethylene glycol 400 0.5% by weight Perfume proper amount water balance (B) 96% ethanol 40% by weight % Example 8 Lipstick A lipstick was prepared according to the following composition. (A)
A part of (B) was added and the mixture was roller-treated to form a pigment part. After heating and dissolving (B), the mixture was homogenized, homogenized and rapidly solidified, and then shaped.

(A) Titanium dioxide 2% by weight N-benzoyl-O-methyl-α-dehydrotyrosine isop 5.7% by weight ropyl ester (B) Hexadecyl alcohol 25% by weight Lanolin 4% by weight Beeswax 5% by weight Ozokerite 4% by weight Candelilla wax 7% by weight % Carnauba wax 2% by weight Antioxidant Proper amount Perfume Proper amount Castor oil Balance Example 9 Oily sun gel A fatty substance is heated at 40 to 45 ° C. according to the following composition, silica is added while stirring this, and an oily sun gel is obtained by cooling. Prepared.

N-benzoyl-O-methyl-α-dehydrotyrosine Lauri 3% by weight Luster p-methoxycinnamic acid 2-ethylhexyl ester 2% by weight Cocoa butter 2.5% by weight Silica 10% by weight Antioxidant proper amount Perfume proper fatty acid triglyceride balance (C _{8 to} C ₁₂ ) Example 10 Foaming air spray 90 parts of a mixture having the following composition and Freon gas (F21 / F114 = 40)
/ 60) 10 parts were put into a pressure resistant container to make a foaming air spray.

4-benzylidene-2,5-dioxo-1-imidazolidinepropionate isopropyl es 0.3% by weight terstearic acid 7% by weight propylene glycol 7% by weight triethanolamine 6% by weight olive oil 2% by weight water balance Example 11 None Foaming lotion air spray 30 parts of a mixture of the following composition and Freon gas (F21 / F114 = 40
/ 60) 70 parts were put in a pressure resistant container to make a non-foaming lotion air spray.

N-acetyl-O-methyl-α-dehydrotyrosine isopro 1% by weight Pyrester propylene glycol 10% by weight 99% Ethanol 30% by weight Water balance Example 12 Foundation (C) was mixed and heated at 70 ° C. according to the following composition ( Oil phase). Separately, (B) is mixed and dissolved and kept at 70 ° C (aqueous phase).
After dispersing (A) in the aqueous phase, an oil phase was further added to emulsify and cool to obtain a foundation.

(A) 4-Benzylidene-2,5-dioxo-1-imidazolidine propionate n-butyle 10% by weight Stell titanium oxide 6% by weight Bengala 1.5% by weight Iron oxide yellow 0.2% by weight (B) N-lauroylglutamine Acid monomagnesium salt 0.5% by weight Triethanolamine 1.4% by weight Propylene glycol 9.5% by weight Water 37.9% by weight (C) Stearic acid 2.8% by weight Propylene glycol monostearate 2.8% by weight Glycerin monostearate 2.8% by weight (self-emulsifying type) Liquid paraffin 24.6% by weight Example 13 White powder White powder was obtained by mixing according to the following composition.

N-benzoyl-O-methyl-α-dehydrotyrosine 72.4% by weight laurylamide talc 10% by weight titanium oxide 1% by weight kaolin 5% by weight Nε-lauroyllysine 5% by weight zinc laurate 1.8% by weight iron oxide (red, yellow) , Black) 1.8% by weight Fragrance 3% by weight Example 14 Rinse After (A) was heated and dissolved at 80 ° C. according to the following composition,
(B) is added and dispersed. Then, (C) previously dissolved at 80 ° C. was added, and the mixture was emulsified and cooled to room temperature to prepare a rinse.

(A) 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1,3-imidazolidine 1% by weight disodium dipropionate cation DS (Note 1) 1% by weight CAE (Note) 2) 0.5 wt% Polyoxyethylene sorbitan monooleate 0.5 wt% (4E.O.) Polyoxyethylene sorbitan monooleate 0.5 wt% (25E.O.) Water 89.5 wt% (B) Nε-lauroyl lysine 2 wt% (4E.O.) C) Liquid paraffin 2% by weight Cetanol 3% by weight (Note 1) Sanyo Chemical Co., Ltd. (Note 2) Ajinomoto Co., Inc.

Claims (1)

[Claims] 1. A cosmetic composition comprising at least one of the compounds represented by the following general formulas (1) and (2). (However, B is a hydrogen atom or an acetyl group. X ₁ ,
X ₂ and X ₃ are either a hydrogen atom, a hydroxyl group, or a methoxy group, and two or three of them may be the same at the same time, or all of them may be different. Y is an oxygen atom or an amino group (-NH-). Z is a methyl group or a phenyl group. R is an alkyl group, a cyclohexyl group C ₃ -C _18, or a trimethylcyclohexyl group. ) (However, in the general formula (2), X ₁ , X ₂ , and X ₃ are each a hydrogen atom, a hydroxyl group, or a methoxy group, and even if two or three of them are the same at the same time, or all of them are the same. W is a hydrogen atom or --CH ₂ --CH ₂ CO ₂ R. R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group or a trimethylcyclohexyl group.)